CN103582524A - Methods for producing epoxidation catalysts and epoxidation methods utilizing them - Google Patents

Methods for producing epoxidation catalysts and epoxidation methods utilizing them Download PDF

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CN103582524A
CN103582524A CN201280027671.6A CN201280027671A CN103582524A CN 103582524 A CN103582524 A CN 103582524A CN 201280027671 A CN201280027671 A CN 201280027671A CN 103582524 A CN103582524 A CN 103582524A
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catalyst
epoxidation
solution
manganese
dipping
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CN103582524B (en
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S·戈帕尔
L·N·V·默西
A·G·巴斯拉尔
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Dow Technology Investments LLC
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    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
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    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/024—Multiple impregnation or coating
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
    • C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
    • C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
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    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
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Abstract

A method for producing epoxidation catalysts is provided. The catalyst comprises a support, a catalytic species, maganese and at least one alkali metal and/or promoter. The catalytic species may be silver. The catalyst is prepared by a method wherein at least a portion of the manganese is impregnated in a step separate from the at least one alkali metal and/or promoter. Advantageously, catalysts produced by the present method may exhibit greater efficiencies than catalysts produced by conventional methods. A method for the epoxidation of alkylenes using the catalysts so produced is provided as is a method for using the alkylene oxides for the production of 1,2-diols, 1,2-carbonates, 1,2-diol ethers, or alka-nolamines.

Description

The method of production epoxidation catalyst and the epoxidizing method that utilizes them
Technical field
The method of producing epoxidation catalyst is provided herein.Described method comprises repeatedly dipping, and the catalyst so producing is estimated to show the efficiency of raising with respect to the catalyst of producing by conventional method.Also provide and utilized the epoxidizing method of the catalyst of preparation like this.
Background technology
Catalyst is the important component of many chemical fabrication processes, and conventionally can be used for accelerating the speed of the reaction discuss and/or improve the selective or efficiency to target product.In conjunction with the utilization in many reactions, catalyst has been found particularly advantageous purposes in the epoxidation of alkene, and the epoxidation of alkene is the technique in Chinese daily chemical articles industry with remarkable commercial significance.In epoxidation reaction, contain at least charging of alkene and oxygen and contact with catalyst, cause the formation of corresponding alkylene oxide.
An example of the alkene epoxidation of special commercial significance is the epoxidation of alkene (alkylene) or alkene mixture, and for viable commercial, this epoxidation reaction relies on high performance catalyst especially.Conventionally, for alkene epoxidation catalyst, comprise separately or be combined and be deposited on the catalytic specie on suitable carrier/carrier with one or more co-catalysts.
For a period of time, those skilled in the art are always in efficiency and/or the activity of actively seeking to improve epoxidation catalyst, for example, even if increase because selective slight in commercial scale, 1%, also can reduce significantly the operating cost relevant with epoxidation technique.
In the research in this field wide range, and, in catalytic component for example carrier, co-catalyst and catalytic specie, catalyst manufacture method and even in the field of epoxidation technique itself, seeking to provide the improvement that catalyst efficiency improves and/or extend service life.Yet further improvement will be welcome in this area.
Expectation, provide and can produce the method that shows the epoxidation catalyst of efficiency raising with respect to conventional catalyst.
Summary of the invention
The invention provides the production method that the epoxidation catalyst of producing with respect to routine shows the epoxidation catalyst of efficiency raising.More particularly, this method provides the selective dipping of catalyst carrier.Surprisingly find now, when at least a portion manganese and other alkali metal and/or co-catalyst separate while being impregnated on carrier, the catalyst generating can show efficiency and improve, for example, than the catalyst of preparing according to conventional method is high, reach 1%.
Therefore,, aspect first, provide the method for manufacturing epoxidation catalyst.Described epoxidation catalyst comprises carrier, at least one catalytic specie, manganese and at least one alkali metal and/or co-catalyst.Described method is included in impregnation steps separates dipping by least a portion manganese and described at least one alkali metal and/or co-catalyst.In some embodiments, described manganese can be combined and be impregnated on carrier with at least one catalytic specie, and described catalytic specie can comprise silver in some embodiments.
The epoxidation catalyst of preparing according to described method is also provided.Described at least one alkali metal and/or co-catalyst can comprise rhenium, sodium, caesium, lithium, sulfate or these combination.In some embodiments, described at least one alkali metal and/or co-catalyst comprise rhenium ideally.In these and other embodiment, described catalytic specie can comprise silver.
Described epoxidation catalyst is estimated to show than high nearly 1% the efficiency of the epoxidation catalyst of producing according to conventional methods.Therefore, also provide alkene process for epoxidation.Described epoxidizing method comprises oxygen source and alkene contacted under epoxidation catalyst exists, and wherein said epoxidation catalyst is prepared by the manganese of amount at least partly being separated to flood with at least one alkali metal and/or co-catalyst in impregnation steps.
The efficiency that shows by described epoxidation catalyst improves to be estimated such as to reduce the material using, the forms such as time that reduce purifying end product, for the product in downstream more provides benefit.Therefore 1,2-glycol, 1,2-glycol ethers, 1, the method for 2-carbonic ester or alkanolamine manufactured be also provided.Described method comprise alkylene oxide is changed into described 1,2-glycol, 1,2-glycol ethers, 1,2-carbonic ester or alkanolamine.The catalyst that utilization is prepared according to described method, prepares alkylene oxide.
Accompanying drawing explanation
When considering following detailed description together with accompanying drawing, can further understand and/or illustrate these and other feature of the present invention, aspect and advantage.
Fig. 1 is conventional epoxidation catalyst and according to the % efficiency of the epoxidation catalyst of a kind of embodiment production of described method, the figure of % outlet ethylene oxide concentration is described;
Fig. 2 is conventional epoxidation catalyst and according to the % efficiency of the epoxidation catalyst of a kind of embodiment production of described method, the figure of % outlet ethylene oxide concentration is described;
Fig. 3 is conventional epoxidation catalyst and according to the % efficiency of the epoxidation catalyst of a kind of embodiment production of described method, the figure of % outlet ethylene oxide concentration is described;
Fig. 4 is conventional epoxidation catalyst and according to the % efficiency of the epoxidation catalyst of a kind of embodiment production of described method, the figure of % outlet ethylene oxide concentration is described;
Fig. 5 is conventional epoxidation catalyst and according to the % efficiency of the epoxidation catalyst of a kind of embodiment production of described method, the figure of % outlet ethylene oxide concentration is described;
Fig. 6 is conventional epoxidation catalyst and according to the % efficiency of the epoxidation catalyst of a kind of embodiment production of described method, the figure of % outlet ethylene oxide concentration is described; With
Fig. 7 is conventional epoxidation catalyst and according to the % efficiency of the epoxidation catalyst of a kind of embodiment production of described method, the figure of % outlet ethylene oxide concentration is described.
The specific embodiment
This description provides some definition and method, to define better the present invention and to instruct those of ordinary skill in the art to implement the present invention.For concrete term or phrase provides or do not provide definition not mean that hint any special importance or there is no importance; But unless otherwise noted, the conventional usage according to those of ordinary skill in association area understood in term.
The technology of using unless otherwise defined, otherwise in this article and scientific terminology and those skilled in the art in the invention conventionally implication of understanding are identical." selectively " of epoxidation reaction, is synonym with " efficiency ", refers to minute rate that forms the conversion of corresponding alkylene oxide product or the alkene of reaction, is expressed as percentage.Term " efficiency " and " selectively " are used interchangeably in this article.The activity of epoxidation reaction can quantize by many modes, a kind of is when temperature of reactor keeps substantial constant, and the alkylene oxide comprising in the outlet of reactor stream is with respect to the molar percentage of the alkylene oxide comprising in inlet streams (in inlet streams the molar percentage of alkylene oxide conventionally but must not approach 0%); To keep the alkylene oxide of given speed to produce needed temperature with another kind.Under many circumstances, activity is measured according to the molar percentage of the alkylene oxide producing under the constant temperature of appointment within a certain period of time.Or activity can be measured as the function that maintains the needed temperature of constant alkylene oxide molar percentage that produces appointment.
Term " first ", " second " etc., do not represent any order, amount or importance while using in this article, but be used for distinguishing an element and another element.Equally, denotion (a not indicating with quantity, an) do not represent quantitative limitation, and mean and have at least one item of censuring, and term " above ", " back side ", " bottom " and/or " top ", unless otherwise noted, only for describe convenient for the purpose of, be not limited to any one position or spatial orientation.If disclose scope, the end points that relates to so all scopes of same composition or character is also (for example can independently combining of inclusive, the scope of " until 25wt%; or more particularly; 5wt% is to about 20wt% " comprises all medians in end points and " 5wt% to 25wt% " scope, etc.).In whole description, mention " a kind of embodiment ", " another kind of embodiment ", " embodiment " etc., refer to that the concrete element (for example feature, structure and/or characteristic) of describing in conjunction with described embodiment is included at least one embodiment described herein, and can or can not be present in other embodiment.In addition, be appreciated that described inventive features can combination in any suitable manner in described various embodiments.
The manufacture method of manufacturing the epoxidation catalyst that comprises carrier, catalytic specie, manganese and alkali metal that at least one is other and/or co-catalyst is provided herein.More particularly, described method requires at least a portion manganese and described at least one other alkali metal and/or co-catalyst separates and separate and be impregnated on selected carrier with described catalytic specie in some embodiments.
Surprisingly find now, by adopting described method, can obtain showing high nearly 1% the catalyst of catalyst that selectivity ratios is prepared by conventional method.That is to say, as long as at least a portion manganese of waiting to be included in described catalyst separates dipping with any other alkali metal and/or the co-catalyst waiting to be included in described catalyst, be expected in the catalyst of preparing by this beneficial effect providing by this method can be provided, irrelevant with used described other alkali metal and/or co-catalyst.
Manganese may be provided in the form of anionic retention aid catalyst, and for example form of oxygen anion (mangaic acid root), or the metal oxygen anion mixing, comprises polyoxy anion structure.Be fully recognized that, many anionic retention aid catalyst have the chemistry of complex and can have one or more forms, any all can the acceptance as the manganese source in this method in them.In addition, also the precursor of known oxygen anion or oxygen anion can be for flooding described carrier in solution, and during described catalyst preparation condition and/or between its operating period, the concrete manganese oxygen anion or the precursor that originally exist can be converted into another kind of form.The accurate manganese material that can finally be present on described catalyst during the present invention does not intend to be used limits.Therefore, exemplary manganese component includes but not limited to manganese acetate, ammonium manganous sulfate, manganese citrate, manganous dithionate, manganese oxalate, manganese nitrate, manganese sulfate and manganese acid radical anion, MnO4 anion for example, and composition thereof.In order to stablize described manganese component in some dipping solution, can add chelate compound, for example ethylenediamine tetra-acetic acid (EDTA) to described dipping solution in some embodiments.
Except manganese, catalyst prepared in accordance with the present invention comprises at least one other alkali metal and/or co-catalyst ideally.As known in the art, there are various known co-catalysts or material, they when the catalysis material with concrete for example silver when existing, be of value to one or more aspects of catalyst performance or otherwise work to promote for example ability of oxirane or expoxy propane of catalyst manufacturing objective product.More particularly, and co-catalyst although it is so itself is not considered to catalysis material conventionally, but they can contribute to one or more beneficial effects of catalyst performance conventionally, for example improve target product throughput rate or amount, reduce the reaction rate reach suitable required temperature, the speed that reduces undesired reaction or amount etc.In addition, and road arrives as known to persons of ordinary skill in the art, and the material that can serve as the co-catalyst of goal response can be the inhibitor of another reaction.For purposes of the invention, co-catalyst is to being conducive to the influential material of overall reaction tool of effective productive target product, no matter whether it can also suppress the simultaneous any competitive reaction of possibility.
Exemplary alkali metal and/or co-catalyst include but not limited to metal ,IIA family of ，IA family metal, rhenium, molybdenum, tungsten, lithium, sulphur, potassium, rubidium, caesium, chromium, titanium, hafnium, zirconium, vanadium, thallium, thorium, tantalum, niobium, calcium, barium, gallium and germanium, and composition thereof.Preferably, described other metal is selected from for example for example calcium and barium of lithium, potassium, sodium, rubidium and caesium and/or IIA family metal of IA family metal.Most preferably it is lithium, potassium, sodium and/or caesium.
Rhenium, molybdenum or tungsten can be suitable as oxygen anion and provide, for example, as high rhenium acid group, molybdate or the tungstate radicle of salt or sour form.The example of co-catalyst, their characteristic, and mix co-catalyst and as the method for a part for catalyst, be described in the U.S. Patent No. 5 of Thorsteinson etc., 187, 140, specifically on the 11st to 15 hurdles, the United States Patent (USP) 6 of Liu etc., 511, 938, the U.S. Patent No. 5 of Chou etc., 504, 053, the U.S. Patent No. 5 of Soo etc., 102, 848, the U.S. Patent No. 4 of Bhasin etc., 916, 243, 4, 908, 343 and 5, 059, 481, and the U.S. Patent No. 4 of Lauritzen, 761, 394, 4, 766, 105, 4, 808, 738, 4, 820, 675 and 4, 833, 261.
In some embodiments, the catalyst of preparing by this method can comprise rhenium and one or more other alkali metal and/or co-catalysts.Rhenium helps the support type silver-containing catalyst of catalysis from U.S. Patent No. 4,761,394 and U.S. Patent No. 4,766,105 understand.In such embodiment, described rhenium component can provide with various forms, for example, and as metal, as covalent compound, as cation or as anion.Providing efficiency and/or the active rhenium material improving uncertain, can be during prepared by catalyst or the component of adding or generating between the operating period as catalyst.
The example of rhenium compound comprises rhenium salt for example oxide and the acid of rhenium halide, zirconyl oxyhalides rhenium, rhenate, perrhenate, rhenium.Yet, also can use alkali metal high rhenium acid salt, ammonium perrhenate, alkaline-earth metal perrhenate, perrhenic acid silver, other perrhenate and rhenium heptoxide.Rhenium heptoxide, Re 2o 7, when water-soluble, be hydrolyzed into perrhenic acid HReO 4, or perrhenic acid.Therefore,, concerning this description, rhenium heptoxide can be considered to high rhenium acid group, i.e. ReO 4.Other metal for example molybdenum and tungsten can show similar chemistry.
The manganese comprising in the catalyst of this method to be stood and any other required co-catalyst and/or alkali metal are ideally to help catalytic amount or effective dose to provide, and such amount is easily determined by those of ordinary skills.The effectively described co-catalyst amount of work to provide one or more character of the catalyst that comprises described co-catalyst to be improved with respect to the catalyst that does not comprise described co-catalyst of this co-catalyst is provided " helping catalytic amount " of certain co-catalyst.The example of catalytic property especially comprises operability (resisting (run-away) out of control), selective, activity, conversion ratio, stability and yield.The catalytic effect that helps that co-catalyst provides can be subject to being permitted multivariable impact, for example the silver of the surface area of reaction condition, catalyst preparation technology, carrier and pore structure and surface chemical property, catalyst and altogether-co-catalyst (co-promoter) content, be present in other cation and anion on catalyst.The existence of other activator, stabilizing agent, co-catalyst, reinforcing agent or other catalyst improver also can affect and help catalytic effect.
The amount of manganese co-catalyst can extensively change, or from 0.0005 to 2 % by weight of the gross weight based on described catalyst, and can be somewhat dependent upon the surface area of described carrier.For example,, when carrier surface area is at 1.0m 2/ g to 1.3m 2in the time of within the scope of/g, the gross weight of the amount of providing of described manganese component based on described catalyst by weight can be for 5ppm at least or at least between 10ppm or 10ppm to 1000ppm or 20ppm and 300ppm.In some embodiments, the manganese amount of interpolation can be every gram of catalyst at least 1.5 micromoles.
Gross weight based on described catalyst, exemplary suitable rhenium amount expectation be 0.0001 % by weight (1ppmw) to 2 % by weight (20,000ppmw), preferably from 0.0005 % by weight (5ppmw) to 0.5 % by weight (5000ppmw).Gross weight based on described catalyst, exemplary suitable caesium amount expectation is 0.005 % by weight to 0.30 % by weight, or from 0.005 % by weight to 0.15 % by weight.Explanation in another way, the weight based on described catalyst, suitable caesium weight range can be for being greater than 200ppm to 1200ppm.Gross weight based on described catalyst, exemplary suitable sulfur content scope expectation is 0.0025 % by weight to 0.15 % by weight, or from 0.001 % by weight to 0.075 % by weight.
Conventionally, such catalyst is loaded catalyst, and can comprise any many known porous fireproof construction or carrier material, as long as no matter select what porous refractory, it is relative inertness under the chemical substance adopting in using the application of shaped porous bodies and processing conditions are existed.Described carrier material and the therefore catalyst based on it can bear sizable temperature and pressure fluctuation in reactor conventionally, may be also important.
The carrier that preparation is suitable for alkylene oxide catalyst has a lot of known methods.The such method of a part is described in for example United States Patent (USP) 4,379,134,4,806,518,5,063,195,5,384,302,6,831,037 etc.For example, by (mixing) raw material that are mixed, extrusion molding, dry and high-temperature calcination, can prepare the alpha-alumina supports of at least 95% purity.In this case, initial raw material generally include one or more and have alpha-alumina of different nature, can be used as loam mould material and burnout materials (normally organic compound) that adhesive adds to provide physical strength, described burnout materials for mixture to remove porosity and/or the pore size distribution that expectation is provided after it during calcining step.Impurity level in the carrier completing is decided by during the raw-material purity used and calcining step their volatilization degree.Common impurity can comprise containing metal and/or the nonmetallic additive of silica, alkali and alkaline earth oxide and trace.
For alkylene oxide catalyst, use the another kind of preparation method of the carrier with suitable especially character to comprise: optionally to mix zirconium silicate and boehmite alumina (AlOOH) and/or gama-alumina, with aluminium oxide described in the mixture peptization containing acidic components and halide anion (preferably fluorine anion) so that the halo aluminium oxide of peptization to be provided, described peptization halo aluminium oxide is shaped to (for example, by extrusion molding or compacting) so that the peptization halo aluminium oxide of shaping to be provided, the peptization halo aluminium oxide of dry described shaping is to provide dry shaping aluminium oxide, and calcine described dry shaping aluminium oxide so that optional adorned alpha-alumina supports particle to be provided.
In one embodiment, the Alpha-alumina that described carrier material comprises at least 80 % by weight also comprises the leachable alkali metal of acid that is less than by weight 30/1000000ths, the leachable alkali-metal concentration of the percentage by weight of described Alpha-alumina and described acid is calculated according to vehicle weight, the leachable alkali metal of wherein said acid be selected from lithium, sodium, potassium, and composition thereof.
The preparation of carrier material can also comprise any other component of any amount of the essential or needs of machining, such as water, acid, adhesive, lubricant, dispersant, pore former, adulterant, modifier etc., as Introduction to the Principles of Ceramic Processing, J.Reed, Wiley Interscience, those that describe in (1988).
Carrier material is 0.5m at least by the surface area that is ideally porous and measurement 2/ g(is 0.7m more preferably 2/ g to 10m 2/ g), the pore volume of measuring is more preferably 0.4cc/g to 2.0cc/g of 0.3cc/g(at least) and mean pore sizes be the carrier of 1 to 50 micron.
" surface area ", while using in this article, refers to the Society60(1938 as Journal of the American Chemical) 309-316 page as described in, by BET(Brunauer, Emmett and Teller) method is by the surface area of radon survey." total pore volume " refers to the pore volume of carrier material and conventionally by mercury porosimetry, measures." porosity " is the ratio of non-entity volume and material cumulative volume.The total pore volume of measuring by mercury porosimetry or water absorption rate can be used for Estimation of porosity by those skilled in the art." mean pore sizes " refers to the corresponding aperture of point at half place of the shaped porous bodies total pore volume having recorded in pore size distribution.
Described carrier material/catalyst can have any that want, suitable shape.The form of conventional normally a plurality of parallel elongate pipes of business fixed bed ethylene oxide reactor (in suitable shell), the external diameter of described pipe be 2 to 7cm and length be 4 to 14m.For the fixed bed reactors for such, it is that 0.1 inch (0.25cm) for example, to the rounded shape of 0.8 inch (2cm), ball, granule, ring, sheet etc. that described carrier material/catalyst will form diameter ideally.
Except described carrier material, manganese and alkali metal and/or co-catalyst that at least one is other, described epoxidation catalyst comprises the catalytic specie that at least one is deposited thereon.Can by described carrier material advantageously the non-limitative example of the catalytic specie of load comprise metal, solid compounds, molecular catalyst, enzyme and these combination.Conventionally, the catalyst that can be used for ethylene epoxidizing utilizes silver as catalytic specie, and silver is preferred in some embodiments of the present invention.
Can use the silver of any expectation catalytic amount, can catalysis for example direct oxidation of ethylene to be become to the silver of any amount of corresponding alkylene oxide with oxygen or oxygen-containing gas.Conventionally, described carrier material will be with one or more silver compound solutions dipping, and described solution is enough to allow the weight of the silver amount on described carrier material of being provided to based on described catalyst be greater than 5%, be greater than 10%, be greater than 15%, be greater than 20%, be greater than 25%, be preferably greater than 27% and more preferably greater than 30 % by weight.Although the silver amount of using does not have concrete restriction, the weight of the silver amount providing in conjunction with described carrier material based on catalyst, can be less than 70% and be more preferably less than 50 % by weight conventionally.
With regard to density, the catalytic specie for example amount of the silver-colored BET surface area with respect to carrier material may be up to few 0.07g/m 2, or up to 0.2g/m 2, or even up to 0.3g/m 2or more.
Although silver granuel degree is important in finished catalyst, scope is not narrow.Suitable silver granuel degree can be at diameter 10 dusts to 10, in the scope of 000 dust.Preferred silver-colored particle size range is greater than 100 dusts to being less than 5,000 dusts from diameter.Ideally, silver be relatively evenly dispersed in described moulding porous body inner, whole and/or on.
Dipping solution can comprise catalytic specie, silver for example, or can only comprise and wish to be impregnated into the co-catalyst on described carrier.For purposes of the invention, needed is at least one impregnation steps, and manganese and any alkali metal that other is wanted/needs and/or co-catalyst are separated to dipping.If will comprise silver in having the dipping solution of manganese, so described silver can be provided in any solvent known in the art or complexing/solubilizer.These example includes but not limited to lactic acid; Ammonia; Alcohol, for example ethylene glycol; And the mixture of amine and amine.An object lesson of dipping solution can be included in the solution of oxalic acid and ethylenediamine and be dissolved into about 30 silver oxides of % by weight silver and the manganese of desired amount.In other embodiments, manganese can be dissolved in separately in the solvent of expectation with the amount of expectation.
By the order of catalytic specie and described at least one other alkali metal and/or co-catalyst impregnated carrier, can change, as long as at least one impregnation steps, a certain amount of manganese deposits respectively with wishing any other alkali metal or the co-catalyst that deposit on described carrier.In some embodiments, the manganese of other amount can be ideally deposited on a certain amount of catalytic specie on carrier and/or other alkali metal or co-catalyst with hope is combined, and is deposited on described carrier.
For example, silver can deposit first separately, then floods separately manganese, then floods simultaneously or sequentially alkali metal and/or the co-catalyst of any other expectation.Or, can in single-steeping, deposit a certain amount of catalytic specie and a certain amount of manganese, and the catalytic specie of other amount can deposit together with one or more alkali metal and/or co-catalyst etc. in other impregnation steps with manganese.Or a certain amount of manganese can be impregnated on carrier, catalytic specie and at least one alkali metal and/or co-catalyst that then dipping is wanted.In other embodiments, described step can be contrary, that is, carrier can be by the solution impregnation that comprises described at least one alkali metal and/or co-catalyst and/or catalytic specie, then by the solution impregnation that comprises manganese.The dipping solution that comprises manganese can or can not comprise a certain amount of catalytic specie.And the dipping of described catalytic specie and otheralkali metal and/or co-catalyst can occur simultaneously or in succession.If used twice or more times dipping, the carrier of dipping is dried or calcining and/or roasting conventionally between each dipping in succession, to guarantee that described metal deposits on carrier.
In one embodiment, use two step dippings.In a first step, with the solution impregnating carrier that comprises solvent or solubilizer, silver-colored solution and manganese.Then, the carrier of dipping for example, is calcined the time of 0.01 hour to 12 hours in air (or other atmosphere, nitrogen, helium and/or steam) under the temperature of 200 ℃ to 600 ℃ and atmospheric pressure.Optionally, before calcining, the carrier of dipping can be dried to remove desolventizing in baking oven.In second step, with containing extra silver compound and helping the carrier flooding described at least one alkali metal of catalytic amount and/or the solution impregnation of co-catalyst.Described carrier and then in air under the temperature of 200 ℃ to 600 ℃ and atmospheric pressure calcining or the roasting time of 0.01 hour to 12 hours.
When for epoxidizing method, the catalyst expection of preparing according to method described herein shows efficiency and reaches 1% than the catalyst producing is according to conventional methods high.Such method generally includes described catalyst exposure in comprising required alkene, oxygen source and the incoming flow of one or more gas phase co-catalysts conventionally.
Gas-phase epoxidation catalyst reaction is considered to be formed the speed of target alkylene oxide and/or for forming target alkylene oxide, suppressed alkene or alkylene oxide oxidation formation carbon dioxide and water by increase, can increase efficiency and/or the activity of epoxidation catalyst.Many such co-catalysts are known, and any in them can be in method of the present invention.Conventionally, the gas phase co-catalyst that can be used for epoxidation reaction includes organic compounds, and particularly including organohalogen compounds, for example bromide or chloride." co-catalyst " is called as " inhibitor " or " moderator (moderator) " sometimes.
In the middle of these, particularly preferably chlorohydrocarbon and bromo-hydrocarbons.These example includes but not limited to chloromethanes, chloroethanes, dichloroethanes, Bromofume, vinyl chloride or these any combination.Particularly preferred gas-phase epoxidation catalyst reaction for this method is chloroethanes and dichloroethanes.
Take that to use chlorohydrocarbon gas phase co-catalyst be example, it is believed that described co-catalyst improves for the efficiency of target alkylene oxide and/or active ability depends on that described gas phase co-catalyst is for example by for example atomic chlorine or chlorion are deposited on the degree of carrying out catalyst surface described in chlorination in the gas phase on catalyst or above described catalyst by specific chloride material.Yet, do not have the hydrocarbon of chlorine atom to be considered to from described catalyst removal chlorine, therefore reduced total raising that described gas phase co-catalyst provides.The discussion of this phenomenon is found in Berty, " Inhibitor Action of Chlorinated Hydrocarbons in the Oxidation of Ethylene to Ethylene Oxide; " Chemical Engineering Communications, Vol.82(1989), 229-232; And Berty, " Ethylene Oxide Synthesis, " Applied Industrial Catalysis, Vol.I(1983), 207-238.Paraffin compound, for example ethane or propane, be considered to effective especially when from Catalyzer in Dechlorination.Yet, alkene, for example ethene and propylene, be also considered to play the effect from Catalyzer in Dechlorination.A part for these hydrocarbon also can be used as impurity in ethylene feed and introduces or can (for example use recirculation flow) for other reasons and exist.Conventionally, the preferred concentration of ethane in charging, when existing, is 0 to 2 % by mole.In view of described gas phase co-catalyst and described non-halo, the non-competitive effect of catalytic hydrocarbon in reactor feed flow that help, be suitable for definition " total halogenation validity value ", it is " total chlorination validity value " in the situation that of organic chloride, helps catalysis and the non-clean effect of catalyzed gas material in the described catalyst of halogenation (or chlorination) that help described in representing.The in the situation that of organic chloride gas phase co-catalyst, total chlorination validity can be defined as nondimensional number Z*, and is expressed from the next:
Figure BDA0000430882600000121
Wherein chloroethanes equivalent is the chloroethane concentration in ppmv, and this concentration in reactor feed flow under organic chloride substrate concentration, provides the catalyst chlorination validity substantially the same with being present in organic chloride in incoming flow; And ethane equivalent is ethane concentration in mol%, under the concentration of this concentration non-chloro-hydrocarbons in incoming flow, provide the Catalyzer in Dechlorination validity substantially the same with non-chloro-hydrocarbons in described incoming flow.
If chloroethanes is to be present in the chloride co-catalyst of gaseous state unique in reactor feed flow, described chloroethanes equivalent is the chloroethane concentration in ppmv.If another kind of chloride co-catalyst (particularly vinyl chloride, chloromethanes or dichloroethanes) separately or use together with chloroethanes, described chloroethanes equivalent is concentration (proofreading and correct for them and the validity that chloroethanes the is compared to co-catalyst mutually) sum in chloroethane concentration with the chloride co-catalyst of described other gaseous state of ppmv.The relative effectiveness of non-chloroethanes co-catalyst can be according to experimental measurement, by replacing chloroethanes with another kind of co-catalyst and measuring for the needed concentration of catalyst performance of the par being provided by chloroethanes is provided.As further illustrating, if in order to realize the equivalent validity of the catalyst performance that 1ppmv chloroethanes provides, the dichloroethanes concentration that reactor inlet place needs is 0.5ppmv, and the chloroethanes equivalent for 1ppmv dichloroethanes will be 2ppmv chloroethanes so.For supposition, have the charging of 1ppmv dichloroethanes and 1ppmv chloroethanes, the chloroethanes equivalent in the molecule of Z* will be 3ppmv.As another example, have been found that for some catalyst, the chlorination validity of chloromethanes is less than 10 times, chloroethanes.Therefore, for such catalyst, for the chloroethanes equivalent of the chloromethanes of given concentration (in ppmv), be, the ppmv concentration of 0.1x(chloromethanes).
The molar percentage concentration that described ethane equivalent is ethane in reactor feed flow adds the concentration of other hydrocarbon effectively dechlorinating from catalyst, has proofreaied and correct described other hydrocarbon phase for the dechlorination validity of ethane.The relative effectiveness of ethene and ethane can be according to experimental measurement, by determine for comprise ethene and ethane the two charging with there is identical ethylene concentration but there is specific chloroethanes equivalent concentration and do not have the same feedstock of ethane to compare, the entrance chloroethanes equivalent concentration of the catalyst performance of par is provided.
As further illustrating, if the ethane concentration of the ethylene concentration that feed composition comprises 30.0 % by mole and 0.30 % by mole, find that but 6.0ppm chloroethanes equivalent level provides the catalyst performance level identical with the similar 3.0ppm chloroethanes equivalent that there is no ethane of feed composition, the ethane equivalent for 30.0 % by mole of ethene will be 0.30 % by mole so.For entrance, reactor feed has for 30.0 % by mole of ethene and 0.3 % by mole of ethane, and ethane equivalent will be 0.6 % by mole.As another kind explanation, have been found that for some catalyst, the dechlorination validity of methane is lower than 500 times, ethane.Therefore,, for such catalyst, the ethane equivalent of methane is % by mole concentration of 0.002x(methane).For conventionally having the entrance reactor feed of 30.0 % by mole of ethene and 0.1 % by mole of ethane, ethane equivalent will be 0.4 % by mole.
The relative effectiveness of the hydrocarbon beyond ethane and ethene can, according to experimental measurement, by under two kinds of different charging ethane concentration, determine that the charging that comprises object hydrocarbon is issued to the needed entrance chloroethanes of same catalyst performance equivalent concentration in its input concentration.If discovery hydrocarbon compound has very little dechlorination effect and exists with low concentration, it can be ignored the centinormal 1 contribution of ethane in Z* calculating so.
Therefore,, in view of above-mentioned relation, in the situation that reactor feed flow comprises ethene, chloroethanes, dichloroethanes, vinyl chloride and ethane, total chlorination validity value of described method can be defined as follows:
( 2 ) Z * = ( ECL + 2 * EDC + VCL ) ( C 2 H 6 + 0.01 * C 2 H 4 )
Wherein ECL, EDC and VCL are respectively in the chloroethanes (C of ppmv in reactor feed flow 2h 5cl), dichloroethanes (Cl-CH 2-CH 2-Cl) and vinyl chloride (H 2c=CH-Cl) concentration.C 2h 6and C 2h 4respectively % by mole concentration of ethane and ethene in reactor feed flow.
Those skilled in the art will recognize that, although can utilize single chlorohydrocarbon co-catalyst in some embodiments of the present invention, but after contacting with described catalyst under epoxidation reaction condition, can form various compounds and therefore be present in described method.Thereby be appreciated that, even if originally utilize in the method a kind of or certain gas phase co-catalyst, but the scope of claim is considered to not only comprise the co-catalyst of introducing, and be included in any or all its product that can form during using said method.
May find in an application of the invention a useful especially class catalyst comprise can be used for alkene epoxidation, especially for alkene or alkene mixture epoxidised those.Many lists of references have been described these reactions, their representative example is the U.S. Patent No. 6 of Liu etc., 511,938 and the U.S. Patent No. 5,057,481 of Bhasin, and Kirk-Othmer ' s Encyclopedia of Chemical Technology, the 4th edition (1994), the 9th, 915-959 page.Although the invention is not restricted to this, for the purpose of simple and explanation, the application of this method is described further by basis with reference to the catalyst that can be used for ethylene epoxidizing.
Surprisingly find now, the epoxidation catalyst of preparing according to method described herein can show efficiency and reach at least 1% than the epoxidation catalyst of preparation is according to conventional methods high.Therefore this method provides obvious cost and saving of time.The form of the conservation of raw material that further cost savings can provide by the catalyst efficiency producing according to described method realizes.
Thereby the present invention also provides the process for epoxidation of alkene.The those of ordinary skill of field of chemical engineering is familiar with such technique.Technique be described in a Kirk-Othmer ' s Encyclopedia of Chemical Technology, the 4th edition, Vol.9,1994,925-939 page.
So generally speaking, described epoxidation reaction can occur in any suitable reactor, for example, and fixed bed reactors, CSTR (CSTR) and fluidized-bed reactor, many in described reactor are well known to a person skilled in the art, need to not describe in detail at this.Recycle unreacted charging or by one pass systems or by adopting the reactor of arranged in series to utilize successive reaction to improve the desirability of conversion of ethylene, also can easily be determined by those skilled in the art.Selected concrete operational mode is subject to process economics to learn domination conventionally.
Normally heat release of epoxidation reaction.Therefore, can provide cooling system (for example, thering is cooling fluid for example coolant jacket or the hydraulic circuit of heat-transfer fluid or boiling water) to regulate the temperature of reactor.Described heat-transfer fluid can be any in some known heat-transfer fluids, for example tetralin (1,2,3,4-naphthane).With boiling in water-cooled reactor, described cooling agent is introduced into the cold side of reactor, the most normally shell-side as aqueous water.When it flows through cold side, described water removes and reduces phlegm and internal heat from process side, and a part of water is vaporized into steam.Described cooling agent leaves the cold side of reactor as the mixture of water and steam.The steam that leaves reactor passes through from its heat extraction and condensation, and the entrance of coolant side is got back in recirculation.In reactor, the temperature of cooling agent is determined by the boiling point of water, and when the boiling point of water is worked by it again, residing pressure determines.Described pressure utilizes ventilation valve to control, and it discharges some pressure from leave the steaming steam-water mixture of reactor cold side.Conventionally, use loop controller, by automatic adjusting ventilation valve, to keep maintaining temperature required necessary pressure, regulate coolant temperature.
Can for example carry out as follows alkene (alkene), optimal ethylene to the conversion of oxyalkylene, optimization ethylene oxide: at the temperature of 200 ℃ to 300 ℃, mass velocity as required and productivity ratio can, under the pressure changing between 5 atmospheric pressure (506kPa) and 30 atmospheric pressure (3.0MPa), be introduced for example, incoming flow containing the gas phase co-catalyst of alkene (ethene) and oxygen or oxygen-containing gas and PPM level to the reactor containing catalyst continuously.Oxygen can or be supplied to described reaction as pure oxygen or as oxygen-enriched air in containing oxygen flow, for example air.Utilize the alkylene oxide that conventional method is separated from product and recovery generates, optimization ethylene oxide.
In described technique, any alkene be can use, may be suitable by epoxidised those example, 1,9-decadinene, 1,3-butadiene, 2-butylene, isobutene, 1-butylene, propylene, ethene or these combination be included but not limited to.Preferably, described alkene comprises ethene.
Conventionally, epoxidation reaction may be carried out ideally in gas phase, and the charging and the epoxidation catalyst that comprise required alkene and oxygen are come in contact.Usually, described catalyst exists as solid material, and more particularly, the packed bed can be used as in predetermined reactor exists.In packed bed, the amount of catalyst can be 10kg at least, or 20kg at least, or from 10 2to 10 7kg or from 10 3to 10 6kg.
Many epoxidation reactions are carried out as continuous process, at this, also so consider.In such process, predetermined reactor can conventionally be equipped with heat-exchange apparatus and control in described process, reactor and/or the temperature of catalyst bed.
Described charging can comprise one or more optional components in addition, comprises, for example, carbon dioxide, inert gas, saturated hydrocarbons etc.When carrying out the recirculation of described charging, can there is carbon dioxide in expection especially, because carbon dioxide is the accessory substance of many epoxidation process.In these embodiments, at least part of carbon dioxide in recycle gas is removed by conventional methods, Kirk-Othmer ' s Encyclopedia of Chemical Technology for example, the 4th edition (1994) the 9th, those modes of describing in 915-959 page, because carbon dioxide has harmful effect to catalyst performance, especially activity.Described inert gas can comprise nitrogen, argon gas or its mixture.Can utilize saturated hydrocarbons for example methane control the heat in reactor and allow the higher oxygen concentration in charging.
In one embodiment, alkene method for oxidation comprises the reaction mixture feed that comprises alkene, oxygen and carbon dioxide contacted with the catalyst of preparing according to provided method, and described catalyst comprises carrier and is deposited on silver, the manganese on described carrier and co-catalyst and/or the alkali metal that at least one is other; Wherein, based on total reaction mixture, the amount of described carbon dioxide in described reactor mixture is maximum 3 % by mole; And described at least one other co-catalyst and/or alkali metal comprise sodium, caesium, lithium, sulfate and composition thereof.
Run duration, the pressure of epoxidation reactor porch can be less than 4000kPa conventionally, or is less than 3500kPa, or preferably will be less than 2500kPa absolute pressure, and in most of the cases will be 1000kPa absolute pressure at least.Gas hourly space velocity (" GHSV ") be standard state temperature and pressure (0 ℃, 1atm) under, the unit volume of passing through the gas of a unit volume catalyst filling bed per hour.Preferably in catalyst filling bed, in gas phase, carry out in those embodiments of epoxidation reaction, startup stage GHSV from 2000 to 10000/ hours ideally.
Run duration, feed composition can remain basically unchanged.More particularly, described reactor inlet oxygen concentration can remain basically unchanged ideally, for example 8 % by mole, described reactor inlet alkene concentration can remain basically unchanged ideally, for example 30 % by mole, described entrance gas concentration lwevel also can remain basically unchanged, for example 3 % by mole, and total catalyst chlorination validity value can remain basically unchanged, for example, when representing with Z*, be 3.
As comprehensible in those skilled in the art, can also regulate other parameter of described epoxidizing method, to reach the expected rate of olefin oxide production during the period of rising and/or reduction temperature.For example, described reactor pressure and/or air speed can be with entrance feed compositions or are changed not together, to be issued to specific throughput rate in specific running temperature.
Or in some embodiments, during epoxidation process, feed composition can change.If needed, reactor inlet oxygen concentration can reduce for example at least 1 % by mole or 2 % by mole or even 3 % by mole, needs only the safe service condition of maintenance and the alkylene oxide output of expectation.Entrance gas concentration lwevel can advantageously improve for example at least 0.5 % by mole or 1 % by mole, and the amount of this increase is that design by epoxidation technique limits in some cases.Total catalyst chlorination validity value for example can advantageously reduce at least 0.5 or even 1.0 or more Z* unit, and the amount of this reduction is that the amount recycling in described technological design limits in some cases.The time period raising with temperature, entrance alkene concentration can keep substantially simultaneously, or, can reduce by 5 or 10 or even 15 % by mole.Under any circumstance, described adjusting or its combination will provide the alkylene oxide level of expectation ideally.
The alkylene oxide producing by this epoxidation process conventionally can be processed, so that other downstream product to be provided, and for example 1,2-glycol, 1,2-glycol ethers, 1,2-carbonic ester and alkanolamine.Because epoxidation catalyst provided by the invention shows the efficiency height at least 1% that efficiency shows than the catalyst producing according to conventional methods, the improvement that expection provides will promote to provide the improvement to these downstream processes and/or product.Therefore also provide herein and produced 1,2-glycol, 1,2-carbonic ester, 1, the improving one's methods of 2-glycol ethers and alkanolamine.
Alkylene oxide is converted into 1,2-glycol or 1,2-glycol ethers can comprise, for example, compatibly, under acid or base catalyst existence, the alkylene oxide of expectation reacts with water.For example, for preferential, produce 1,2-glycol surpasses 1,2-glycol ethers, described alkylene oxide can with the water of ten times of molar excess in liquid phase reactor for example, under acid catalyst (sulfuric acid that is 0.5-1.0wt% based on total reaction mixture) exists, react at 1 bar absolute pressure and 50-70 ℃, or at 130-240 ℃ and 20-40, cling to and depress absolutely, preferably in the situation that there is no catalyst, do not react in gas-phase reaction.If the ratio of water reduces, in reactant mixture 1, the ratio of 2-glycol ethers will improve.Produce like this 1,2-glycol ethers can comprise diether, three ethers, tetraether or other polyether.Or 1,2-glycol ethers can be by with alcohol alkylene oxide or prepare by substituting at least a portion water with described alcohol described in methyl alcohol or ethanol conversion for example.Consequent 1,2-glycol and glycol ethers can be in various final uses application in the industries such as food, beverage, tobacco, cosmetics, thermoplastic polymer, curable resin system, detergent, heat-exchange system.
The alkylene oxide that the catalyst that use produces according to the present invention produces is converted into alkanolamine and can comprises, for example, and by described alkylene oxide and ammonia react.Can use anhydrous or water-based ammonia, but anhydrous ammonia is conducive to monoalkanolamine, and it can use when preferred monoalkanolamine.The alkanolamine generating can be for for example processing natural gas.Alkylene oxide can be transformed into by described alkylene oxide and carbon dioxide reaction corresponding 1,2-carbonic ester.If needed, can be by subsequently will be described 1,2-carbonic ester reacts formation 1,2-glycol and prepares 1,2-glycol with water or alcohol.Method applicatory is with reference to US-6, and 080,897.
The catalyst of describing in following examples is prepared on the carrier of following characteristic with table 1 demonstration:
Table 1 – carrier data
? A B
Size (OD, inch) 0.32-0.36 0.32-0.36
Surface area (m2/g) 1.28 1.03
Pore volume (ml/g) 0.69 0.68
Mean pore sizes (micron) 2.0 2.6
< 1 micron of hole (%) 11.5 6.0
Crushing strength (lbs) 21.4 19.6
embodiment 1
Kaolinite Preparation of Catalyst 1(contrast as described below), all co-catalysts are adding during silver dipping for the second time.The dipping for the first time of carrier A (10.30g) utilizes 30mL roughly to carry out as " catalyst preparation (Catalyst Preparation) " in US2009/177000A1 lower silver-amine-oxalate solution (26.6wt%Ag) described and that prepare.
More particularly, described carrier floods in the suitable glass container of size, and described glass container is equipped with for flood the piston of described carrier under vacuum.For filling the separatory funnel of dipping solution, by rubber stopper, insert the top of steeper.The steeper that contains described carrier is evacuated to about 1-2, and " mercury absolute pressure reaches 15 minutes, then, by opening the piston between separatory funnel and steeper, to described carrier, slowly adds dipping solution.Enter after steeper (approximately 15 seconds) all solution is emptying, discharge vacuum and also pressure is turned back to atmospheric pressure.After adding described solution, described carrier remains in described dipping solution and soaks 15 minutes under environmental condition, then discharges unnecessary solution 15 minutes.
Then the carrier that following roasting silver floods, to realize the reduction of silver on catalyst surface.The carrier spherolite of wet dipping launches at the online single berth of the stainless steel metal with 3mm hole, and is put on the nozzle that connects hot air gun (Steinel HL1610S).Calcination procedure was comprised of two stages.In the first stage, described impregnated carrier at the temperature of 300 ℃ with 75LPM/in 2air-flow roasting 1.5 minutes; Then at second stage, temperature is brought up to 400 ℃, for time 2 minutes, to complete roasting.Air-flow during second roasting stage is 130LPM/in 2.Complete after roasting, cooled catalyst is to room temperature and weigh in the open.
Then utilize the solution of preparing by the co-catalyst solution of the amount that table 1 provides below 40.7g silver-amine-oxalate solution is added, carry out the dipping for the second time of the catalyst spherolite of institute's roasting, described silver-amine-oxalate solution is combined and forms with fresh silver-amine-oxalate solution by the solution from dipping discharge for the first time.Mn (NO 3) 2solution before it adds silver-amine-oxalate solution to (NH 4) 2eDTA complexing.The dipping flooding for the second time for this, discharge opeing and calcination steps and for the first time dipping carry out similarly.Table 1 has provided the discharge opeing and the catalyst after roasting 1 that according to the amount of the co-catalyst solution of silver-colored intake and interpolation, calculate and has formed.
Catalyst 2(the present invention) use the target formulation same with catalyst 1 preparation, unique and difference catalyst 1 be manganese co-catalyst with (NH 4) 2after EDTA complexing, during Ag dipping, adding together with silver for the first time.All other co-catalysts are adding during Ag dipping for the second time.Upper table 1 has provided the final composition of the catalyst 2 calculating according to the co-catalyst amount of solution of silver-colored intake and interpolation.
The Performance Ratio that Fig. 1 has shown catalyst 1 and catalyst 2 in epoxidation of ethylene above.Catalyst is tested (one-pass operation) in the stainless steel reaction organ pipe of 1/4 inch (external diameter).The crushing catalyst (granularity 30/50 order) of 0.7g amount divides with granularity the Denstone(inertia that rate is identical, from Norton Inc, USA) with 1:1(by weight) fully mix, and pack described reactor tube into.Feed composition is: 30 % by mole of ethene, 8 % by mole of oxygen, 1.5 % by mole of carbon dioxide, 0.7 % by mole of ethane, and the chloroethanes of various ppmv levels.Regulate main entrance gas flow rate, not produce 10000h to crushing catalyst -1gas hourly space velocity.The about 1950kPa gauge pressure of reactor pressure.Described catalyst moves under the steady temperature of identical feed composition and 240 ℃.Z* changes by chloroethanes (ECL) concentration changing in charging; The figure of Fig. 1 has shown that outlet EO concentration and oxygen efficiency are along with Z* changes and changes.Maximum (peak) oxygen efficiency obtaining with catalyst of the present invention (catalyst 2) is than the height about 1% obtaining with comparative catalyst's (catalyst 1).
Embodiment 2
Catalyst 3(the present invention) use the target formulation preparation same with catalyst 1, the difference unique with catalyst 1 is that described sodium co-catalyst is adding to described Ag solution during silver dipping for the first time.All other co-catalysts are adding during Ag dipping for the second time.Table 1 has provided the amount of the co-catalyst solution adding to silver-amine-oxalate solution during described impregnation steps and has formed according to the final catalyst calculating of the co-catalyst solution of silver-colored intake and interpolation.
The Performance Ratio that Fig. 2 has shown catalyst 1 and catalyst 3 in epoxidation of ethylene.Charging Z* changes as described in Example 1 and observes response.The maximum oxygen efficiency obtaining with catalyst of the present invention (catalyst 3) is than the high 0.5-0.6% obtaining with comparative catalyst's (catalyst 1).
Embodiment 3
Catalyst 4(contrast) using the target formulation preparation same with catalyst 1, is to described Ag solution, to add sodium co-catalyst and manganese co-catalyst (with (NH during silver dipping for the first time with the unique difference of catalyst 1 4) 2eDTA complexing).Remaining co-catalyst is adding in described silver-amine-oxalate solution during Ag dipping for the second time.Table 1 has provided the amount of the co-catalyst solution adding to silver-amine-oxalate solution during described impregnation steps and has formed according to the final catalyst calculating of the co-catalyst solution of silver-colored intake and interpolation.
The Performance Ratio that Fig. 3 has shown catalyst 1 and catalyst 4 in epoxidation of ethylene.Charging Z* changes as described in Example 1 and observes response.The maximum oxygen efficiency obtaining with catalyst 4 is lower by 1.3% than what obtain with catalyst 1 surprisingly.
As illustrated in embodiment 1 and 2, in the dipping of Ag for the first time, add Mn or Na provides improved efficiency; Yet, as described in Example 3, in the dipping of Ag for the first time, add Mn together and Na is unfavorable to efficiency.
Embodiment 4
Catalyst 5(contrast) preparation is that all co-catalysts are in adding during silver dipping for the second time.Table 1 has provided the final composition of the described catalyst that adds the amount of co-catalyst solution in silver-amine-oxalate solution to during dipping for the second time and calculate according to the co-catalyst amount of solution of silver-colored intake and interpolation.
Catalyst 6(the present invention) use the target formulation preparation same with catalyst 5, the difference unique with catalyst 5 is during silver dipping, to described Ag solution, to add sodium co-catalyst for the first time.All other co-catalysts are adding during Ag dipping for the second time.The final calculating that table 1 has provided catalyst 6 forms.
The Performance Ratio that Fig. 4 has shown catalyst 5 and catalyst 6 in epoxidation of ethylene.Charging Z* changes as described in Example 1 and observes response.The maximum oxygen efficiency obtaining with catalyst of the present invention (catalyst 5) is than the high 0.5-0.6% obtaining with comparative catalyst's (catalyst 5).
Embodiment 5
Catalyst 7(the present invention) use the target formulation preparation same with catalyst 1, the difference unique with catalyst 1 is during silver dipping, to described Ag solution, to add sodium and lithium co-catalyst for the first time.Other co-catalyst is adding during Ag dipping for the second time.Table 1 has provided the amount of the co-catalyst solution adding to silver-amine-oxalate solution during described impregnation steps and according to the composition of the final catalyst 7 calculating of the co-catalyst solution of silver-colored intake and interpolation.
The Performance Ratio that Fig. 5 has shown catalyst 1 and catalyst 7 in epoxidation of ethylene.Charging Z* changes as described in Example 1 and observes response.The maximum oxygen efficiency obtaining with catalyst 7 is than the height about 1.4% obtaining with catalyst 1.
In the second step that adds Li and Na and separating in the dipping of Ag for the first time, add Mn, improved efficiency as illustrated in embodiment 5 is provided.Yet, as described in Example 3, in the dipping of Ag for the first time, add together Mn and Na is disadvantageous to efficiency.
Embodiment 6
Catalyst 8(the present invention) use the target formulation preparation same with catalyst 1, the difference unique with catalyst 1 is to naked carrier, to add manganese co-catalyst before dipping Ag solution.Described catalyst preparation is comprised of following steps.By adding 0.0348g manganese nitrate solution (0.1552g Mn/g solution) to 30g deionized water, preparation Mn solution.Carrier described in 10.13g (A carrier) utilizes above-mentioned solution for vacuum dipping.After discharging unnecessary solution, carrier described in roasting.Then utilize the silver-amine-oxalate solution that contains 25.60wt%Ag to carry out vacuum impregnation for the second time.After Ag dipping, the weight of described catalyst is 13.16g, and Ag load capacity is 23.07%.Then utilize the solution being prepared as follows to carry out the another single-steeping of described calcined catalyst spherolite: to 42.3g silver-amine-oxalate solution, to add 0.0902g CsOH solution (0.4564g Cs/g solution), 0.0944g lithium acetate solution (0.023g Li/g solution), 0.0375g sodium acetate solution (0.071g Na/g solution), 0.8042g ammonium perrhenate solution (0.0359g Re/g solution), 0.0366g ammonium sulfate (0.2789g SO 4/ g solution), 0.0357g manganese nitrate solution (0.1552g Mn/g solution).The dipping of this impregnation steps, discharge opeing and calcination steps and dipping early carry out similarly.After discharge opeing and roasting, final catalyst weight is 15.79g.The composition of the catalyst 8 calculating according to the co-catalyst amount of solution of silver-colored intake and interpolation is Ag:35.71wt%, Cs:627ppm, Li:33ppm, Na:41ppm, Re:439ppm, SO 4: 155ppm, Mn:82ppm.
The Performance Ratio that Fig. 6 has shown catalyst 1 and catalyst 8 in epoxidation of ethylene.Charging Z* changes as described in Example 1 and observes response.The maximum oxygen efficiency obtaining with catalyst 8 is higher by 1% than what obtain with catalyst 1.
Embodiment 7
Catalyst 9(contrast) Ag dipping is only carried out in preparation one time.The solution impregnation that 10.34g carrier spherolite (A carrier) utilization is prepared as follows: add 0.0541g CsOH solution (0.4564g Cs/g solution), 0.0605g lithium acetate solution (0.023g Li/g solution), 0.0245g sodium acetate solution (0.071g Na/g solution), 0.4823g ammonium perrhenate solution (0.0359g Re/g solution), 0.0212g ammonium sulfate (0.2789g SO containing silver-amine-oxalate solution of 18.76wt%Ag to 42.0g 4/ g solution), 0.0238g manganese nitrate solution (0.1552g Mn/g solution) and 0.0947g EDTA bis-ammonium salt solutions (0.4128g EDTA/g solution).Described dipping, discharge opeing and calcination steps and preparation are early carried out similarly.After discharge opeing and roasting, final catalyst weight is 12.30g.The composition of the catalyst 9 calculating according to the co-catalyst amount of solution of silver-colored intake and interpolation is Ag:15.94wt%, Cs:499ppm, Li:28ppm, Na:35ppm, Re:350ppm, SO 4: 120ppm, Mn:75ppm.
Catalyst 10(the present invention) use the preparation preparation same with catalyst 10, the difference unique with catalyst 10 is to described carrier, to add manganese co-catalyst before dipping Ag and other co-catalyst.Described catalyst preparation is comprised of following steps.By adding 0.0334g manganese nitrate solution (0.1552g Mn/g solution) to 30g deionized water, preparation Mn solution.Utilize above-mentioned solution for vacuum dipping 10.26g carrier (A carrier), discharge unnecessary solution roasting spherolite.Utilize subsequently the solution being prepared as follows to carry out another single-steeping: the silver-amine that contains 18.76wt%Ag to 42.0g-oxalate solution is added 0.0503g CsOH solution (0.4564g Cs/g solution), 0.0560g lithium acetate solution (0.023g Li/g solution), 0.0227g sodium acetate solution (0.071g Na/g solution), 0.4477g ammonium perrhenate solution (0.0359g Re/g solution), 0.0200g ammonium sulfate (0.2789g SO 4/ g solution).Described dipping, discharge opeing and calcination steps and preparation are early carried out similarly.After discharge opeing and roasting, final catalyst weight is 12.23g.The composition of the catalyst 10 calculating according to the co-catalyst amount of solution of silver-colored intake and interpolation is Ag:16.13wt%, Cs:499ppm, Li:28ppm, Na:35ppm, Re:349ppm, SO 4: 121ppm, Mn:113ppm.
Fig. 7 shows that example catalyst 10 provides than the starting efficiency of high 0.6 – 0.7% of described comparative catalyst 9.
Table 1
Catalyst numbering
Figure BDA0000430882600000231
Figure BDA0000430882600000241
Figure BDA0000430882600000251
The selection of the co-catalyst that the digital proof presenting will be added in the dipping of Ag is not for the first time footy.In described same step, need the selection of the co-catalyst that adds together and should not mix but the co-catalyst that adds in the step of separating neither be footy.

Claims (11)

1. for the manufacture of the method for the epoxidation catalyst that comprises carrier, at least one catalytic specie, manganese and at least one alkali metal and/or co-catalyst, described method comprises:
In impregnation steps, manganese described at least a portion and described at least one alkali metal and/or co-catalyst are separated to dipping.
2. the process of claim 1 wherein described at least one catalytic specie dipping for described manganese.
3. the process of claim 1 wherein that described at least one alkali metal and/or co-catalyst comprise sodium, caesium, lithium, sulfate or these combination.
4. the process of claim 1 wherein that described at least one alkali metal and/or co-catalyst comprise sodium and flood in the step of separating with described manganese.
5. the process of claim 1 wherein that described manganese comprises Mn-EDTA complex compound.
6. the process of claim 1 wherein that described at least one alkali metal and/or co-catalyst comprise rhenium.
7. the process of claim 1 wherein that described catalytic specie comprises silver.
8. the epoxidation catalyst of preparing according to the method for claim 1.
9. for one or more alkene process for epoxidation, it is included under the epoxidation catalyst existence of preparing according to the method for claim 1 oxygen source is contacted with alkene.
10. the method for claim 8, wherein said alkene comprises ethene.
11. for the manufacture of 1,2-glycol, 1,2-glycol ethers, 1, and the method for 2-carbonic ester or alkanolamine, described method comprises and the alkylene oxide of preparing according to the method for claim 6 is changed into 1,2-glycol, 1,2-glycol ethers, 1,2-carbonic ester or alkanolamine.
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